Methods of improving, optimizing, or maximizing proppant suspension during formation fracturing

ABSTRACT

Compositions and methods of fracturing including a hydrophobic rendered proppant or a proppant slurry and a fracturing fluid including an aqueous base fluid, a viscosifying agent or mixture of viscosifying agents, and an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures thereof, and optionally a crosslinking agent or a mixture of crosslinking agents.

RELATED APPLICATIONS

This application is a divisional application of U.S. patent application Ser. No. 16/857,534 filed Apr. 24, 2020 (24 Apr. 2020), which claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 62/896,877 filed May 2, 2019 (2 May 2019).

BACKGROUND OF THE INVENTION 1. Field of the Invention

Embodiments of the present disclosure relate to compositions for improving, optimizing, or maximizing proppant suspension in fracturing fluids including treated extremely hydrophobic proppant and methods for making and using same.

More particularly, embodiments of the present disclosure relate to compositions for improving, optimizing, or maximizing proppant suspension in fracturing fluids including hydrophobic proppant and methods for making and using same, wherein the composition includes a fracturing fluid including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof and/or a viscosifying agent or mixture of viscosifying agents such as polysaccharides, a suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures thereof, a hydrophobically modified proppant or a hydrophobically modified proppant slurry, optionally a hydrophobic proppant coating composition, optionally a crosslinking agent or a mixture of crosslinking agents, and optionally a crosslinking delay agent or a mixture of crosslinking delay agents.

2. Description of the Related Art

Recently the use of systems and methods for suspending hydrophobically modified proppant with the current technology during hydraulic fracturing operations has been applied mainly in using fresh, brackish and produced water with mixed results on hydrophobically modified proppant suspension, buoyancy and/or fluffiness.

Historically, hydrophobically modified proppants have been disclosed by U.S. Pat. Nos. 7,723,274; 9,714,371; 9,976,075; and 10,023,786. In these patents, proppant modification was accomplished using a plurality of silicon containing compounds such as organosiloxane, organosilane, fluoro-organosiloxane and fluoro-organosilane compounds. In all cases, the compounds changed the wettability of the proppant making the proppant “extremely hydrophobic”, wherein extremely means that the contact angle of water on the treated solid substrate is greater than about 90°.

While many systems and methods have been purposed and used for hydrophobically modified proppant suspension, there is still a need in the art for other new and novel compositions and methods for hydrophobically modified proppant suspension in fracturing fluid using brackish waters, produced water, or other waters having medium or high total dissolved solids and/or medium to high concentrations of hard water components.

SUMMARY OF THE DISCLOSURE

Proppant Suspending Compositions

Embodiments of this disclosure provide hydrophobically modified proppant suspending compositions including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof present in an effective amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the hydrophobically modified proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Fracturing Fluid Compositions

Embodiments of this disclosure provide fracturing fluid compositions including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof, a viscosifying agent or mixture of viscosifying agents such as polysaccharides present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, optionally a crosslinking agent or a mixture of crosslinking agents, and optionally a crosslinking delay agent or a mixture of crosslinking delay agents, wherein the effective amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the fracturing fluid compositions include hydrophobically modified proppant in a fracturing fluid carrier including brackish waters, produced waters, or other waters having medium or high total dissolved solids and/or medium to high concentrations of hard water components.

Embodiments of this disclosure provide fracturing fluid compositions including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof and/or a viscosifying agent or mixture of viscosifying agents such as polysaccharides present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, a hydrophobically modified proppant, optionally a crosslinking agent or a mixture of crosslinking agents, and optionally a crosslinking delay agent or a mixture of crosslinking delay agents, wherein the effective amount is between about 1 ppm and about 1,000 ppm. In certain embodiments, the fracturing fluid compositions also include hydrophobic proppant modifying composition. In other embodiments, the aqueous base fluids include brackish waters, produced waters, or other waters having medium or high total dissolved solids and/or medium to high concentrations of hard water components.

Methods for Making Proppant Suspending Compositions

Embodiments of this disclosure provide methods of making hydrophobically modified proppant suspending compositions including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof, a viscosifying agent or mixture of viscosifying agents such as polysaccharides present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, optionally a crosslinking agent or a mixture of crosslinking agents, and optionally a crosslinking delay agent or a mixture of crosslinking delay agents, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the fracturing fluid compositions include a hydrophobic proppant modifying composition. In other embodiments, the aqueous base fluids include brackish waters, produced waters, or other waters having medium or high total dissolved solids and/or medium to high concentrations of hard water components.

Methods for Making Fracturing Fluid Compositions

Embodiments of this disclosure provide methods of making fracturing fluids including forming a fracturing fluid including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof, a viscosifying agent or mixture of viscosifying agents such as polysaccharides present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, a hydrophobically modified proppant, optionally a crosslinking agent or a mixture of crosslinking agents, and optionally a crosslinking delay agent or a mixture of crosslinking delay agents, wherein the effective in an amount between about 1 ppm and about 1,000 ppm.

Embodiments of this disclosure provide methods of making fracturing fluids including forming a first fracturing fluid including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof, a viscosifying agent or mixture of viscosifying agents such as polysaccharides present in an amount between about 0.01% v/v to about 1.00% v/v, optionally a crosslinking agent or a mixture of crosslinking agents, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof and optionally a crosslinking delay agent or a mixture of crosslinking delay agents, wherein the effective in an amount between about 1 ppm and 1,000 ppm. The methods also include forming a carrier solution and a hydrophobically modified proppant, wherein the carrier solution includes a hydrophobic proppant coating composition.

Methods for Fracturing Formations

Embodiments of this disclosure provide methods of fracturing a formation including pumping or injecting a fracturing fluid including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer such as polyacrylamides and derivatives thereof, a viscosifying agent or mixture of viscosifying agents such as polysaccharides present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, a hydrophobically modified proppant, optionally a crosslinking agent or a mixture of crosslinking agents, and optionally a crosslinking delay agent or a mixture of crosslinking delay agents under fracturing conditions, wherein the effective in an amount between about 1 ppm and 1,000 ppm and wherein the fracturing conditions. In certain embodiments, the methods also include spraying a hydrophobic proppant coating composition into the proppant prior adding the proppant to a fracturing fluid carrier including an aqueous base fluid includes brackish waters, produced waters, or other waters having medium or high total dissolved solids and/or medium to high concentrations of hard water components.

BRIEF DESCRIPTION OF THE DRAWINGS OF THE DISCLOSURE

The disclosure can be better understood with reference to the following detailed description together with the appended illustrative drawings in which like elements are numbered the same:

FIG. 1 depicts a photograph of a control composition including 0.5% v/w of a silicon proppant coating composition.

FIG. 2 depicts a photograph of a hydrophobically modified proppant suspending composition including 0.5% v/w of a silicon proppant coating composition and 50 ppm of a proppant suspending composition.

FIG. 3 depicts a photograph of a control composition including 1.0% v/w of a silicon proppant coating composition.

FIG. 4 depicts a photograph of a hydrophobically modified proppant suspending composition including 1.0% v/w of a silicon proppant coating composition and 50 ppm of a proppant suspending composition.

FIG. 5 depicts a plot of CaCO₃ scaling tendencies.

FIG. 6 depicts a plot of solubility of CaCO₃.

DEFINITIONS OF TERM USED IN THE DISCLOSURE

The following definitions are provided in order to aid those skilled in the art in understanding the detailed description of the present disclosure.

The term “about” means that the value is within about 10% of the indicated value. In certain embodiments, the value is within about 5% of the indicated value. In certain embodiments, the value is within about 2.5% of the indicated value. In certain embodiments, the value is within about 1% of the indicated value. In certain embodiments, the value is within about 0.5% of the indicated value.

The term “substantially” or “essentially” means that the value is within about 5% of the indicated value. In certain embodiments, the value is within about 2.5% of the indicated value. In certain embodiments, the value is within about 1% of the indicated value. In certain embodiments, the value is within about 0.5% of the indicated value. In certain embodiments, the value is within about 0.1% of the indicated value.

The term “fracturing” refers to the process and methods of breaking down a geological formation, i.e. the rock formation around a well bore, by pumping fluid at very high pressures, in order to increase production rates from a hydrocarbon reservoir. The fracturing methods of this disclosure use otherwise conventional techniques known in the art.

The term “proppant” refers to a granular substance suspended in the fracturing fluid during the fracturing operation, which serves to keep the formation from closing back down upon itself once the pressure is released. Proppants envisioned by the present disclosure include, but are not limited to, conventional proppants familiar to those skilled in the art such as sand (e.g., about 20 to about 40 mesh sand, about 30 to about 50 mesh sand, about 100 mesh sand, etc.), resin-coated sand, sintered bauxite, glass beads, and similar materials.

The term_resin coated proppant_means any proppant coated with a resin or polymeric material such as resin coated proppants from CARBO Ceramics Inc., Hexion, Fairmount Santrol, or other resin coated proppants.

The term “hydrophobic proppant” or “hydrophobically modified proppant” means any proppant coated with a polymer to render the proppant hydrophobic such as coating a silicon containing compound.

The term “fracturing layer” is used to designate a layer, or layers, of rock that are intended to be fractured in a single fracturing treatment. It is important to understand that a fracturing layer may include one or more than one of rock layers or strata as typically defined by differences in permeability, rock type, porosity, grain size, Young's modulus, fluid content, or any of many other parameters. That is, a fracturing layer is the rock layer or layers in contact with all the perforations through which fluid is forced into the rock in a given treatment. The operator may choose to fracture, at one time, a fracturing layer that includes water zones and hydrocarbon zones, and/or high permeability and low permeability zones (or even impermeable zones such as shale zones) etc. Thus, a fracturing layer may contain multiple regions that are conventionally called individual layers, strata, zones, streaks, pay zones, etc., and we use such terms in their conventional manner to describe parts of a fracturing layer. Typically, the fracturing layer contains a hydrocarbon reservoir, but the methods may also be used for fracturing water wells, storage wells, injection wells, etc. Note also that some embodiments of the disclosure are described in terms of conventional circular perforations (for example, as created with shaped charges), normally having perforation tunnels. However, the disclosure is may also be practiced with other types of perforations, for example openings or slots cut into the tubing by jetting.

The term “fracturing conditions” means conditions of a fluid temperature up to 350° F., a fluid injection pressure up to about 15,000 pounds per square inch (psi), fluid injection rate up to 150 barrels per minute. In other situations, fracturing conditions pertain to conditions under which an oil and gas wells are fractured to increase gas and oil production from the well. The operating pressures may vary significantly. For example, oil and gas wells may cycle from a shut-in condition, in which the pressure within the well is maintained at a maximum, to a producing condition, in which the pressure within the well is much lower. Further, the flowing conditions can change resulting in cycles of a higher or lower pressure within the well. This “pressure cycling” of a hydraulically fractured well is known to cause damage to proppant in the fracture due to rearrangement and re-stressing of the proppant grains. This results in a less conductive proppant pack in the fracture and adversely impacts production performance of the well. Consequently, a proppant that is resistant to pressure cycling conductivity loss is desirable. The conditions may include temperature, pressure and injection rate. The temperature is generally the well temperature, but heated or cooled fracturing fluids may be used to change the temperature. The pressures, while varying based on formation type, generally is greater than about 10,000 psi. In other embodiments, greater than about 15,000 psi. In other embodiments, greater than about 20,000 psi. In other embodiments, greater than about 25,000 psi. In other embodiments, greater than about 30,000 psi. The injection rate is designed to maintain the fracturing pressures during the fracturing operations, which may include a single injection or a plurality of injections, generally in a periodic manner. Completion conditions may be the same or different from fracturing conditions, but again will depend on the formation to be fractured.

The term “mixture” means an intimate combination of two or more components.

The term “combination_means a use of two material together, but not an intimate mixture such as using two different fluids components that are not mixed beforehand.

The term “plurality” means two or more, more than two, greater than or equal to 2 (∃2).

The term “at least one” means one or a plurality, one or more, greater than or equal to 1 (∃1).

The term “gpt” means gallons per thousand gallons.

The term “ppt” means pounds per thousand gallons.

The term “wt. %” or “w/w” means percent by weight.

The term “vol. %” or “v/v” means percent by volume.

The term “v/w” means volume of a substance per unit of weight (mass) of another component.

DETAILED DESCRIPTION OF THE DISCLOSURE

The inventors have found that a new approach for hydrophobically modified proppant suspension including adding an effective amount of an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective amount is between about 1 ppm and about 1,000 ppm.

The inventors have also found that a method to model and understand the potential increase of the propped surface area, a fully integrated hydraulic fracturing, reservoir, and wellbore simulator with a black oil model has been developed. The model utilized a standard completion design under reservoir conditions to visualize and predict the potential increase in the propped surface area with and without the surface modified extremely hydrophobically proppant. Well A was modeled with a modified proppant suspension additive and Well B without. The fracture planes of Well A yielded almost two to four times more propped surface area than Well B at 100% coating efficiency under the reservoir conditions.

Embodiments of this disclosure broadly relate to enhancing hydrophobically modified proppant suspending compositions include an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof present effective in an amount between about 1 ppm and 1,000 ppm. In certain embodiments, the enhancing proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Embodiments of this disclosure broadly relate to fracturing fluid compositions including an aqueous base fluid having a total dissolved solids above about 5,000 ppm, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, and an effective amount of an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the compositions also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the enhancing proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Embodiments of this disclosure broadly relate to fracturing fluid compositions including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures and combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, a hydrophobically modified proppant, and a hydrophobic proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof. In certain embodiments, the enhancing proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the proppant comprises sand, a particulate ceramic, a resin coated sand, or mixtures and combinations thereof. In other embodiments, the fracturing fluid compositions may also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents.

Embodiments of this disclosure broadly relate to methods of making hydrophobically modified proppant suspending compositions including blending an aqueous base fluid, and an effective amount of a hydrophobically modified proppant suspending composition hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the compositions may also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the hydrophobically modified proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Embodiments of this disclosure broadly relate to methods of making fracturing fluids including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, and a hydrophobically modified proppant suspending composition proppant, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the fracturing fluids may also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the hydrophobically modified proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Embodiments of this disclosure broadly relate to methods of making fracturing fluids including forming a first fracturing fluid including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, and an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm, and forming a second fracturing fluid including a proppant carrier solution and a proppant, wherein the proppant carrier solution includes a hydrophobic proppant coating composition. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the fracturing fluids may also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the hydrophobically modified proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Embodiments of this disclosure broadly relate to methods of fracturing a formation including pumping or injecting a fracturing fluid including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, a hydrophobically modified proppant, and a proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof, under fracturing conditions, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, in the pumping step, the fluid further may also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the hydrophobically modified proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Embodiments of this disclosure broadly relate to methods of fracturing a formation including pumping a first fracturing fluid including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, and an effective amount of a hydrophobically modified proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, under fracturing conditions, wherein the effective in an amount between about 1 ppm and about 1,000 ppm, and pumping a second fracturing fluid including a proppant carrier fluid and a hydrophobically modified proppant. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the fracturing fluid may also include a crosslinking agent or a mixture of crosslinking agents, and/or a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, in the second pumping step, the proppant carrier fluid further including a proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof. In other embodiments, the hydrophobically modified proppant suspending compositions do not include a quaternary salt of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between about 5 and about 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Proppant Suspending Compositions

Embodiments of this disclosure relate to proppant suspending compositions comprising an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the composition is adapted to be present in an effective amount between about 1 ppm and 1,000 ppm in an aqueous based fracturing fluid, wherein the aqueous base fluid include at least 5,000 ppm total dissolved solids, and wherein the composition does not include an ammonium based quaternary salt. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the aldehydes are selected from the group consisting of (a) C₁ aldehydes including formaldehyde (CH₂O); (b) C₂ aldehydes including glyoxylic acid (C₂H₂O₃), chloroacetaldehyde (C₂H₃ClO), glyoxal (C₂H₂O₂), glycolaldehyde (C₂H₄O₂), fluoroacetaldehyde (C₂H₃FO), chloral (C₂HCl₃O), or acetaldehyde (C₂H₄O); (c) C₃ aldehydes including propionaldehydes or propanals (C₃H₆O), glyceraldehyde (C₃H₆O₃), malondialdehyde (C₃H₄O₂), lactaldehyde (C₃H₆O₂), or methylglyoxal (C₃H₄O₂);(d) C₄ aldehydes including butyraldehydes or butanals (C₄H₈O), succinaldehyde (C₄H₆O₂), 3-hydroxybutanal (C₄H₈O₂), isobutyraldehyde (C₄H₈O), or g-hydroxybutyraldehyde (C₄H₈O₂); (e) C₅ aldehydes including pentanals (C₅H₁₀O), trans-2-methyl-2-butenal (C₅H₈O), furfural (C₅H₄O₂), glutaconaldehyde (C₅H₆O₂), glutaraldehyde (C₅H₈O₂), isovaleraldehyde (C₅H₁₀O), or pivaldehyde (C₅H₁₀O); (f) C₆ aldehydes including hexanals (C₆H₁₂O), hydroxymethylfurfural (C₆H₆O₃), or cis-3-hexenal (C₆H₁₀O); (g) C₇ aldehydes including heptanals (C₇H₁₄O), phenolic aldehyde (C₇H₆O₂), methoxymethylfurfural (C₇H₈O₃), tetrahydrobenzaldehyde (C₇H₁₀O), or benzaldehyde (C₇H₆O); (h) C₈ aldehydes including octanals (C₈H₁₆O), phenylglyoxal (C₈H₆O₂), 3,4-dihydroxyphenylacetaldehyde (C₈H₈O₃), or phenylacetaldehyde (C₈H₈O); (i) C₉ aldehydes including nonanals (C₉H₁₈O), 2-nitrocinnamaldehyde (C₉H₇O₃N), 4-oxo-2-nonenal (C₉H₁₄O₂), cinnamaldehyde (C₉H₈O), or 4-hydroxynonenal (C₉H₁₆O₂); (j) C₁₀ aldehydes including decanals (C₁₀H₂₀O), citral (C₁₀H₁₆O), hydroxycitronellal (C₁₀H₂₀O₂), 4-methoxycinnamaldehyde (C₁₀H₁₀O₂), safranal (C₁₀H₁₄O), 8-oxogeranial (C₁₀H₁₄O₂), or citronellal (C₁₀H₁₈O); (k) C₁₁ aldehydes including undecanals (C₁₁H₂₂O), helional (C₁₁H₁₂O₃), nitrophenyl pentadienal (C₁₁H₉NO₃), or sinapaldehyde (C₁₁H₁₂O₄); (l) C₁₂ aldehydes including dodecanals (C₁₂H₂₄O); (m) C₁₃ aldehydes including tridecanals (C₁₃H₂₆O), bourgeonal (C₁₃H₁₈O), or hydroxymethylpentylcyclohexenecarboxaldehyde (C₁₃H₂₂O₂); (n) C₁₄ aldehydes including tetradecanes (C₁₄H₂₈O) or lilial (C₁₄H₂₀O); (o) C₁₅ aldehydes including pentadecanes (C₁₅H₃₀O), hexyl cinnamaldehyde (C₁₅H₂₀O), abscisic aldehyde (C₁₅H₂₀O₃), velleral (C₁₅H₂₀O₂), or polygodial (C₁₅H₂₂O₂); (p) C₁₆ aldehydes including hexadencanals (C₁₆H₃₂O) or callicarpenal (C₁₆H₂₆O); (q) C₁₇ aldehydes including hetadecanals (C₁₇H₃₄O), botrydial (C₁₇H₂₆O₅), or oleocanthal (C₁₇H₂₀O₅); (r) C₁₈ aldehydes including octadecanals (C₁₈H₃₆O); (s) C₁₉ aldehydes including nonadecanals (C₁₉H₃₈O); (t) C₂₀ aldehydes including icosanals (C₂₀H₄₀O) or retinal (C₂₀H₂₈O), substituted analogous thereof, and mixtures or combinations thereof, (u) substituted analogous thereof, and (v) mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion.

Fracturing Fluids Including a Proppant Suspending Composition

Embodiments of this disclosure relate to fracturing fluid compositions comprising (a) an aqueous base fluid having a total dissolved solids above about 5,000 ppm, (b) a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, and (c) an effective amount of an proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the aldehydes are selected from the group consisting of (a) C₁ aldehydes including formaldehyde (CH₂O); (b) C₂ aldehydes including glyoxylic acid (C₂H₂O₃), chloroacetaldehyde (C₂H₃ClO), glyoxal (C₂H₂O₂), glycolaldehyde (C₂H₄O₂), fluoroacetaldehyde (C₂H₃FO), chloral (C₂HCl₃O), or acetaldehyde (C₂H₄O); (c) C₃ aldehydes including propionaldehydes or propanals (C₃H₆O), glyceraldehyde (C₃H₆O₃), malondialdehyde (C₃H₄O₂), lactaldehyde (C₃H₆O₂), or methylglyoxal (C₃H₄O₂);(d) C₄ aldehydes including butyraldehydes or butanals (C₄H₈O), succinaldehyde (C₄H₆O₂), 3-hydroxybutanal (C₄H₈O₂), isobutyraldehyde (C₄H₈O), or g-hydroxybutyraldehyde (C₄H₈O₂); (e) C₅ aldehydes including pentanals (C₅H₁₀O), trans-2-methyl-2-butenal (C₅H₈O), furfural (C₅H₄O₂), glutaconaldehyde (C₅H₆O₂), glutaraldehyde (C₅H₈O₂), isovaleraldehyde (C₅H₁₀O), or pivaldehyde (C₅H₁₀O); (f) C₆ aldehydes including hexanals (C₆H₁₂O), hydroxymethylfurfural (C₆H₆O₃), or cis-3-hexenal (C₆H₁₀O); (g) C₇ aldehydes including heptanals (C₇H₁₄O), phenolic aldehyde (C₇H₆O₂), methoxymethylfurfural (C₇H₈O₃), tetrahydrobenzaldehyde (C₇H₁₀O), or benzaldehyde (C₇H₆O); (h) C₈ aldehydes including octanals (C₈H₁₆O), phenylglyoxal (C₈H₆O₂), 3,4-dihydroxyphenylacetaldehyde (C₈H₈O₃), or phenylacetaldehyde (C₈H₈O); (i) C₉ aldehydes including nonanals (C₉H₁₈O), 2-nitrocinnamaldehyde (C₉H₇O₃N), 4-oxo-2-nonenal (C₉H₁₄O₂), cinnamaldehyde (C₉H₈O), or 4-hydroxynonenal (C₉H₁₆O₂); (j) C₁₀ aldehydes including decanals (C₁₀H₂₀O), citral (C₁₀H₁₆O), hydroxycitronellal (C₁₀H₂₀O₂), 4-methoxycinnamaldehyde (C₁₀H₂₀O), safranal (C₁₀H₁₄O), 8-oxogeranial (C₁₀H₁₄O₂), or citronellal (C₁₀H₁₈O); (k) C₁₁ aldehydes including undecanals (C₁₁H₂₂O), helional (C₁₁H₁₂O₃), nitrophenyl pentadienal (C₁₁H₉NO₃), or sinapaldehyde (C₁₁H₁₂O₄); (l) C₁₂ aldehydes including dodecanals (C₁₂H₂₄O); (m) C₁₃ aldehydes including tridecanals (C₁₃H₂₆O), bourgeonal (C₁₃H₁₈O), or hydroxymethylpentylcyclohexenecarboxaldehyde (C₁₃H₂₂O₂); (n) C₁₄ aldehydes including tetradecanes (C₁₄H₂₈O) or lilial (C₁₄H₂₀O); (o) C₁₅ aldehydes including pentadecanes (C₁₅H₃₀O), hexyl cinnamaldehyde (C₁₅H₂₀O), abscisic aldehyde (C₁₅H₂₀O₃), velleral (C₁₅H₂₀O₂), or polygodial (C₁₅H₂₂O₂); (p) C₁₆ aldehydes including hexadencanals (C₁₆H₃₂O) or callicarpenal (C₁₆H₂₆O); (q) C₁₇ aldehydes including hetadecanals (C₁₇H₃₄O), botrydial (C₁₇H₂₆O₅), or oleocanthal (C₁₇H₂₀O₅); (r) C₁₈ aldehydes including octadecanals (C₁₈H₃₆O); (s) C₁₉ aldehydes including nonadecanals (C₁₉H₃₈O); (t) C₂₀ aldehydes including icosanals (C₂₀H₄₀O) or retinal (C₂₀H₂₈O), substituted analogous thereof, and mixtures or combinations thereof, (u) substituted analogous thereof, and (v) mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the fracturing fluid further includes a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, or a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and a crosslinking delay agent or a mixture of crosslinking delay agents.

Embodiments of this disclosure relate to fracturing fluid compositions comprising (a) an aqueous base fluid having a total dissolved solids above about 5,000 ppm, (b) a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, (c) an effective amount of an proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures and combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm, (d) one or more proppant, and (e) optionally a hydrophobic proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof, wherein the proppant is precoated or coated in a slurry prior to blending with the hydrophobic proppant coating composition. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the aldehydes are selected from the group consisting of (a) C₁ aldehydes including formaldehyde (CH₂O); (b) C₂ aldehydes including glyoxylic acid (C₂H₂O₃), chloroacetaldehyde (C₂H₃ClO), glyoxal (C₂H₂O₂), glycolaldehyde (C₂H₄O₂), fluoroacetaldehyde (C₂H₃FO), chloral (C₂HCl₃O), or acetaldehyde (C₂H₄O); (c) C₃ aldehydes including propionaldehydes or propanals (C₃H₆O), glyceraldehyde (C₃H₆O₃), malondialdehyde (C₃H₄O₂), lactaldehyde (C₃H₆O₂), or methylglyoxal (C₃H₄O₂);(d) C₄ aldehydes including butyraldehydes or butanals (C₄H₈O), succinaldehyde (C₄H₆O₂), 3-hydroxybutanal (C₄H₈O₂), isobutyraldehyde (C₄H₈O), or g-hydroxybutyraldehyde (C₄H₈O₂); (e) C₅ aldehydes including pentanals (C₅H₁₀O), trans-2-methyl-2-butenal (C₅H₈O), furfural (C₅H₄O₂), glutaconaldehyde (C₅H₆O₂), glutaraldehyde (C₅H₈O₂), isovaleraldehyde (C₅H₁₀O), or pivaldehyde (C₅H₁₀O); (f) C₆ aldehydes including hexanals (C₆H₁₂O), hydroxymethylfurfural (C₆H₆O₃), or cis-3-hexenal (C₆H₁₀O); (g) C₇ aldehydes including heptanals (C₇H₁₄O), phenolic aldehyde (C₇H₆O₂), methoxymethylfurfural (C₇H₈O₃), tetrahydrobenzaldehyde (C₇H₁₀O), or benzaldehyde (C₇H₆O); (h) C₈ aldehydes including octanals (C₈H₁₆O), phenylglyoxal (C₈H₆O₂), 3,4-dihydroxyphenylacetaldehyde (C₈H₈O₃), or phenylacetaldehyde (C₈H₈O); (i) C₉ aldehydes including nonanals (C₉H₁₈O), 2-nitrocinnamaldehyde (C₉H₇O₃N), 4-oxo-2-nonenal (C₉H₁₄O₂), cinnamaldehyde (C₉H₈O), or 4-hydroxynonenal (C₉H₁₆O₂); (j) C₁₀ aldehydes including decanals (C₁₁₀H₂₀O), citral (C₁₀H₁₆O), hydroxycitronellal (C₁₀H₂₀O₂), 4-methoxycinnamaldehyde (C₁₀H₁₀O₂), safranal (C₁₀H₁₄O), 8-oxogeranial (C₁₀H₁₄O₂), or citronellal (C₁₀H₁₈O); (k) C₁₁ aldehydes including undecanals (C₁₁H₂₂O), helional (C₁₁H₁₂O₃), nitrophenyl pentadienal (C₁₁H₉NO₃), or sinapaldehyde (C₁₁H₁₂O₄); (l) C₁₂ aldehydes including dodecanals (C₁₂H₂₄O); (m) C₁₃ aldehydes including tridecanals (C₁₃H₂₆O), bourgeonal (C₁₃H₁₈O), or hydroxymethylpentylcyclohexenecarboxaldehyde (C₁₃H₂₂O₂); (n) C₁₄ aldehydes including tetradecanes (C₁₄H₂₈O) or lilial (C₁₄H₂₀O); (o) C₁₅ aldehydes including pentadecanes (C₁₅H₃₀O), hexyl cinnamaldehyde (C₁₅H₂₀O), abscisic aldehyde (C₁₅H₂₀O₃), velleral (C₁₅H₂₀O₂), or polygodial (C₁₅H₂₂O₂); (p) C₁₆ aldehydes including hexadencanals (C₁₆H₃₂O) or callicarpenal (C₁₆H₂₆O); (q) C₁₇ aldehydes including hetadecanals (C₁₇H₃₄O), botrydial (C₁₇H₂₆O₅), or oleocanthal (C₁₇H₂₀O₅); (r) C₁₈ aldehydes including octadecanals (C₁₈H₃₆O); (s) C₁₉ aldehydes including nonadecanals (C₁₉H₃₈O); (t) C₂₀ aldehydes including icosanals (C₂₀H₄₀O) or retinal (C₂₀H₂₈O), substituted analogous thereof, and mixtures or combinations thereof, (u) substituted analogous thereof, and (v) mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the fracturing fluid further includes a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, or a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the one or more proppants are precoated or coated in a slurry with a hydrophobic proppant treating composition to form hydrophobically modified proppants, and the hydrophobic proppant treating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.

Methods of Making

Embodiments of this disclosure relate to methods of making fracturing fluids comprising blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents present in an amount between about 0.01% v/v to about 1.00% v/v, an effective amount of an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and about 1,000 ppm, and a hydrophobically modified proppant. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the fracturing fluid further includes a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, or a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the one or more proppants are precoated or coated in a slurry with a hydrophobic proppant treating composition to form hydrophobically modified proppants, and the hydrophobic proppant treating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.

Methods of Fracturing

Embodiments of this disclosure relate to methods of making fracturing fluids comprising: forming a first fracturing fluid including blending an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents, and an effective amount of an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and 1,000 ppm, and forming a second fracturing fluid including a proppant carrier solution including a hydrophobic rendering proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof, and a proppant to form a hydrophobically modified proppant. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the fracturing fluid further includes a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, or a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the one or more proppants are precoated or coated in a slurry with a hydrophobic proppant treating composition to form hydrophobically modified proppants, and the hydrophobic proppant treating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.

Embodiments of this disclosure relate to methods of fracturing a formation comprising pumping or injecting, under fracturing conditions, a fracturing fluid including an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents, an effective amount of an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and 1,000 ppm, one or more proppants, and a hydrophobic rendering proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof to form a hydrophobically modified proppant, wherein the proppant is precoated or coated in a slurry prior to blending with other components. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the fracturing fluid further includes a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, or a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the one or more proppants are precoated or coated in a slurry with a hydrophobic proppant treating composition to form hydrophobically modified proppants, and the hydrophobic proppant treating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.

Embodiments of this disclosure relate to methods of fracturing a formation comprising pumping, under fracturing conditions, a first fracturing fluid including: an aqueous base fluid, a friction reducer or a mixture of friction reducers, a high viscosity friction reducer or mixtures of high viscosity friction reducer and/or a viscosifying agent or mixture of viscosifying agents, and an effective amount of an enhancing proppant suspending composition including an aldehyde, a mixture of aldehydes, a ketone, a mixture of ketones, or mixtures or combinations thereof, wherein the effective in an amount between about 1 ppm and 1,000 ppm, and pumping, under fracturing conditions, a second fracturing fluid including: a proppant carrier fluid including a hydrophobic rendering proppant coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof and a proppant to form a hydrophobically modified proppant. In certain embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In certain embodiments, the aldehydes are compounds of the formula R—CHO, wherein R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, and the ketones are compounds of the formula R′ B C(O) B R″, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), one or more of the carbon atoms may be replaced by oxygen atoms. In other embodiments, the aldehydes are selected from the group consisting of formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, and the ketones are selected from the group consisting of acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof. In other embodiments, the quaternary salt comprises compounds of the general formula R¹R²R³ArN⁺X^(!), wherein R¹, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X^(!) is a counterion. In other embodiments, the aqueous base fluid comprises a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof. In other embodiments, the fracturing fluid further includes a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, or a crosslinking agent or a mixture of crosslinking agents including borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and a crosslinking delay agent or a mixture of crosslinking delay agents. In other embodiments, the one or more proppants are precoated or coated in a slurry with a hydrophobic proppant treating composition to form hydrophobically modified proppants, and the hydrophobic proppant treating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.

Compositional Ranges of the Disclosure

Proppant Suspending Compositions

Embodiments of this disclosure include a proppant suspending composition including between about 1 ppm and about 1,000 ppm, between about 1 ppm and about 900 ppm, between about 1 ppm and about 800 ppm, between about 1 ppm and about 700 ppm, between about 1 ppm and about 600 ppm, between about 1 ppm and about 500 ppm, between about 1 ppm and about 400 ppm, between about 1 ppm and about 300 ppm, between about 1 ppm and about 200 pmm, between about 1 ppm and about 100 pmm, between about 5 ppm and about 100 pmm, between about 10 ppm and about 100 pmm, between about 15 ppm and about 100 pmm, between about 20 ppm and about 100 pmm, between about 25 ppm and about 100 pmm, and any value within the ranges.

Fracturing Fluids

Generally, a fracturing fluid treatment involves pumping a low or high viscosity fluid into a formation including a proppant, although the proppant may be pumped-in later, as a free viscous fluid, or pad, usually water with some fluid additives to generate high viscosity, into a formation at a rate faster than the fluid can escape into the formation so that the pressure rises and the rock of the formation fractures or breaks, creating artificial fractures and/or enlarging existing fractures. During or after fracturing the formation, the propping agent, generally a solid material such as sand is added to the fluid to form a slurry that is pumped into the newly formed fractures in the formation to prevent them from closing when the pumping pressure is released.

The liquid carrier can generally be any liquid carrier suitable for use in oil and gas producing wells. In certain embodiments, the liquid carrier is water and an aqueous base fluid wherein water is typically the major component by weight of the fluid. The water can be potable or non-potable water. The water can be brackish or contain other materials typical of sources of water found in or near oil fields. For example, it is possible to use fresh water, brine, or even water to which any salt, such as an alkali metal or alkali earth metal salt (NaCl, KCl, etc.) has been added.

Suitable Reagents/Devices Used in the Disclosure

Aldehydes

Suitable aldehydes for use in the present disclosure include, without limitation, linear, branched, saturated, unsaturated, cyclic, or aromatic aldehydes of the general formula R—CHO, where R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), wherein one or more of the carbon atoms may be replaced by oxygen atoms. Exemplary aldehydes include, without limitation, formaldehydes, ethanal, propanal, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal, pentadecanal, higher alkanals, and substituted analogs thereof. Other aldehydes include, without limitation: (a) C₁ aldehydes including formaldehyde (CH₂O); (b) C₂ aldehydes including glyoxylic acid (C₂H₂O₃), chloroacetaldehyde (C₂H₃ClO), glyoxal (C₂H₂O₂), glycolaldehyde (C₂H₄O₂), fluoroacetaldehyde (C₂H₃FO), chloral (C₂HCl₃O), or acetaldehyde (C₂H₄O); (c) C₃ aldehydes including propionaldehydes or propanals (C₃H₆O), glyceraldehyde (C₃H₆O₃), malondialdehyde (C₃H₄O₂), lactaldehyde (C₃H₆O₂), or methylglyoxal (C₃H₄O₂); (d) C₄ aldehydes including butyraldehydes or butanals (C₄H₈O), succinaldehyde (C₄H₆O₂), 3-hydroxybutanal (C₄H₈O₂), isobutyraldehyde (C₄H₈O), or g-hydroxybutyraldehyde (C₄H₈O₂); (e) C₅ aldehydes including pentanals (C₅H₁₀O), trans-2-methyl-2-butenal (C₅H₈O), furfural (C₅H₄O₂), glutaconaldehyde (C₅H₆O₂), glutaraldehyde (C₅H₈O₂), isovaleraldehyde (C₅H₁₀O), or pivaldehyde (C₅H₁₀O); (f) C₆ aldehydes including hexanals (C₆H₁₂O), hydroxymethylfurfural (C₆H₆O₃), or cis-3-hexenal (C₆H₁₀O); (g) C₇ aldehydes including heptanals (C₇H₁₄O), phenolic aldehyde (C₇H₆O₂), methoxymethylfurfural (C₇H₈O₃), tetrahydrobenzaldehyde (C₇H₁₀O), or benzaldehyde (C₇H₆O); (h) C₈ aldehydes including octanals (C₈H₁₆O), phenylglyoxal (C₈H₆O₂), 3,4-dihydroxyphenylacetaldehyde (C₈H₈O₃), or phenylacetaldehyde (C₈H₈O); (i) C₉ aldehydes including nonanals (C₉H₁₈O), 2-nitrocinnamaldehyde (C₉H₇O₃N), 4-oxo-2-nonenal (C₉H₁₄O₂), cinnamaldehyde (C₉H₈O), or 4-hydroxynonenal (C₉H₁₆O₂); (j) C₁₀ aldehydes including decanals (C₁₀H₂₀O), citral (C₁₁₀H₁₆O), hydroxycitronellal (C₁₀H₂₀O₂), 4-methoxycinnamaldehyde (C₁₀H₁₀O₂), safranal (C₁₀H₁₄O), 8-oxogeranial (C₁₀H₁₄O₂), or citronellal (C₁₀H₁₈O); (k) C₁₁ aldehydes including undecanals (C₁₁H₂₂O), helional (C₁₁H₁₂O₃), nitrophenyl pentadienal (C₁₁H₉NO₃), or sinapaldehyde (C₁₁H₁₂O₄); (l) C₁₂ aldehydes including dodecanals (C₁₂H₂₄O); (m) C₁₃ aldehydes including tridecanals (C₁₃H₂₆O), bourgeonal (C₁₃H₁₈O), or hydroxymethylpentylcyclohexenecarboxaldehyde (C₁₃H₂₂O₂); (n) C₁₄ aldehydes including tetradecanes (C₁₄H₂₈O) or lilial (C₁₄H₂₀O); (o) C₁₅ aldehydes including pentadecanes (C₁₅H₃₀O), hexyl cinnamaldehyde (C₁₅H₂₀O), abscisic aldehyde (C₁₅H₂₀O₃), velleral (C₁₅H₂₀O₂), or polygodial (C₁₅H₂₂O₂); (p) C₁₆ aldehydes including hexadencanals (C₁₆H₃₂O) or callicarpenal (C₁₆H₂₆O); (q) C₁₇ aldehydes including hetadecanals (C₁₇H₃₄O), botrydial (C₁₇H₂₆O₅), or oleocanthal (C₁₇H₂₀O₅);(r) C₁₈ aldehydes including octadecanals (C₁₈H₃₆O); (s) C₁₉ aldehydes including nonadecanals (C₁₉H₃₈O); (t) C₂₀ aldehydes including icosanals (C₂₀H₄₀O) or retinal (C₂₀H₂₈O), (u) substituted analogous thereof, and (v) mixtures or combinations thereof.

Ketones

Suitable ketones for use in the present disclosure include, without limitation, linear, branched, saturated, unsaturated, cyclic, or aromatic ketones of the general formula R′ B C(O) B R′, wherein R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), wherein one or more of the carbon atoms may be replaced by oxygen atoms. Exemplary ketones include, without limitation, acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, and substituted analogs thereof.

Synthetic Hydratable Polymers

Suitable synthetic hydratable polymers for use in the present invention include, without limitation, (a) polyvinyl alcohol polymers and copolymers, (b) polyacrylamide polymers and copolymers, (c) poly-2-amino-2-methyl propane sulfonic acid polymers (AMPS) and copolymers, (d) polyacrylic acid polymers and copolymers, (e) polymethacrylic acid polymers and copolymers, (f) high molecular weight homo- and/or copolymers of acrylic acid crosslinked with polyalkenyl polyethers, (g) high molecular weight hydrophobically modified, cross-linked polyacrylate polymers, (h) hydrophilic, anionic, high molecular weight, cross-linked polyacrylic acid polymers, (i) for those polymers that have hydrolyzable groups, the polymers may be hydrolyzed to any desired degree, and (j) mixtures or combinations thereof.

Natural Hydratable Polymers

Suitable natural hydratable water soluble polymers for use in this invention include, without limitation, polysaccharides and mixtures or combinations thereof. Suitable polysaccharides include galactomannan gum and cellulose derivatives. In certain embodiments, the polysaccharides include guar gum, locust bean gum, carboxymethylguar, hydroxyethylguar, hydroxypropylguar, carboxymethylhydroxypropylguar, carboxymethylhydroxyethylguar, hydroxymethyl cellulose, carboxymethylhydroxyethyl cellulose, and hydroxyethyl cellulose and mixtures or combinations thereof.

The natural hydratable polymer useful in the present invention can be any of the hydratable polysaccharides having galactose or mannose monosaccharide components and are familiar to those in the well service industry. These polysaccharides are capable of gelling in the presence of a crosslinking agent to form a gelled based fluid. For instance, suitable hydratable polysaccharides are the galactomannan gums, guars, and derivatized guars. Specific examples are guar gum and guar gum derivatives. Suitable gelling agents are guar gum, hydroxypropyl guar and carboxymethyl hydroxypropyl guar. In certain embodiment, the hydratable polymers for the present invention are guar gum and carboxymethyl hydroxypropyl guar and hydroxypropyl guar. Other exemplary fracturing fluid formulations are disclosed in U.S. Pat. Nos. 5,201,370 and 6,138,760, which are incorporated herein by reference. In other embodiments, the hydratable natural polysaccharides include, without limitation, guar gum, guar gum derivatives, locust bean gum, Karaya gum, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, or mixtures and combinations thereof. In other embodiments, the hydratable natural polysaccharides include, without limitation, guar gums, hydroxypropyl guar, carboxymethyl hydroxypropyl guar, carboxymethyl guar, carboxymethyl hydroxyethyl cellulose, or mixtures and combinations thereof.

Friction Reducers

Suitable friction reducers and high viscosity friction reduces include, without limitation, polyacrylamide polymers and copolymers.

Proppants

The proppant type can be sand, intermediate strength ceramic proppants (available from Carbo Ceramics, Norton Proppants, etc.), sintered bauxites and other materials known to the industry. Any of these base propping agents can further be coated with a resin (available from Santrol, a Division of Fairmount Industries, Borden Chemical, etc.) to potentially improve the clustering ability of the proppant. In addition, the proppant can be coated with resin or a proppant flowback control agent such as fibers for instance can be simultaneously pumped. By selecting proppants having a contrast in one of such properties such as density, size and concentrations, different settling rates will be achieved. Also resin coated proppants from CARBO Ceramics Inc., Hexion, Fairmount Santrol, or other resin coated proppants.

Propping agents or proppants are typically added to the fracturing fluid prior to the addition of a crosslinking agent. However, proppants may be introduced in any manner which achieves the desired result. Any proppant may be used in embodiments of the invention. Examples of suitable proppants include, but are not limited to, quartz sand grains, glass and ceramic beads, walnut shell fragments, aluminum pellets, nylon pellets, and the like. Proppants are typically used in concentrations between about 1 to 8 lbs. per gallon of a fracturing fluid, although higher or lower concentrations may also be used as desired. The fracturing fluid may also contain other additives, such as surfactants, corrosion inhibitors, mutual solvents, stabilizers, paraffin inhibitors, tracers to monitor fluid flow back, and so on.

Besides the proppant concentrations in the final formulation, the particles sizes of the proppants are also a factor in the performance of the fluids of this invention. In certain embodiments, the proppants have sizes of 16/20 mesh, 16/30 mesh, 20/40 mesh and mixtures and combinations thereof. In addition, proppant density is another factor in the performance of the fluids of this invention. Exemplary examples of the proppants useful in this invention include, without limitation, CARBO-HSP⁷ 16/30 mesh and 20/40 mesh having a bulk density=2 g/cm³ and CARBO-LITE⁷ 16/20 mesh and 20/40 mesh having a bulk density=1.57 g/cm³, and mixtures or combinations thereof.

Aqueous Base Fluids

Suitable aqueous base fluids includes, without limitation, seawater, brackish water, produced water, flowback water, water including one or more water soluble salts such as metal chloride, metal phosphates, metal sulfates, metal, or makeup water containing up to about 30% crude oil, or mixtures thereof, wherein the metals are alkali metals, alkaline metals, transition metals or mixtures and combinations thereof.

Other Additives

The fracturing fluids of this invention can also include other additives as well such as scale inhibitors, carbon dioxide control additives, paraffin control additives, oxygen control additives, biocides, gel stabilizers, surfactants, clay control additives, or other additives.

Scale Control

Suitable additives for Scale Control and useful in the compositions of this invention include, without limitation: chelating agents, e.g., Na⁺, K⁺ or NH4 salts of EDTA; Na⁺, K⁺ or NH4 salts of NTA; Na⁺, K⁺ or NH4 salts of Erythorbic acid; Na⁺, K⁺ or NH4 salts of thioglycolic acid (TGA); Na⁺, K⁺ or NH4 salts of Hydroxy acetic acid; Na⁺, K⁺ or NH4 salts of Citric acid; Na, K or NH4 salts of Tartaric acid or other similar salts or mixtures or combinations thereof. Suitable additives that work on threshold effects, sequestrants, include, without limitation: Phosphates, e.g., sodium hexamethylphosphate, linear phosphate salts, salts of polyphosphoric acid, Phosphonates, e.g., nonionic such as HEDP (hydroxythylidene diphosphoric acid), PBTC (phosphoisobutane, tricarboxylic acid), amino phosphonates of: MEA (monoethanolamine), NH₃, EDA (ethylene diamine), bishydroxyethylene diamine, bisaminoethylether, DETA (diethylenetriamine), HMDA (hexamethylene diamine), hyper homologues and isomers of HMDA, Polyamines of EDA and DETA, Diglycolamine and homologues, or similar polyamines or mixtures or combinations thereof; phosphate esters, e.g., polyphosphoric acid esters or phosphorus pentoxide (P₂O₅) esters of: alkanol amines such as MEA, DEA, triethanol amine (TEA), bishydroxyethylethylene diamine; ethoxylated alcohols, glycerin, glycols such as EG (ethylene glycol), propylene glycol, butylene glycol, hexylene glycol, trimethylol propane, pentaeryithrol, neopentyl glycol or the like; tris & tetra hydroxy amines; ethoxylated alkyl phenols (limited use due to toxicity problems), and ethoxylated amines such as monoamines such as MDEA and higher amines from 2 to 24 carbons atoms, diamines 2 to 24 carbons carbon atoms, or the like.

Paraffin Control

Suitable additives for use in the fracturing fluids of this invention for paraffin removal, dispersion, and/or paraffin crystal distribution include, without limitation: cellosolves available from dow chemicals company; cellosolve acetates; ketones; acetate and formate salts and esters; surfactants composed of ethoxylated or propoxylated alcohols, alkyl phenols, and/or amines; methylesters such as coconate, laurate, soyate or other naturally occurring methylesters of fatty acids; sulfonated methylesters such as sulfonated coconate, sulfonated laurate, sulfonated soyate or other sulfonated naturally occurring methylesters of fatty acids; or mixtures or combinations thereof. Suitable alcohols used in preparation of the surfactants include, without limitation, linear or branched alcohols, specially, mixtures of alcohols reacted with ethylene oxide, propylene oxide or higher alkyleneoxide, wherein the resulting surfactants have a range of HLBs. Suitable alkylphenols used in preparation of the surfactants include, without limitation, nonylphenol, decylphenol, dodecylphenol or other alkylphenols wherein the alkyl group has between about 4 and about 30 carbon atoms. Suitable amines used in preparation of the surfactants include, without limitation, ethylene diamine (EDA), diethylenetriamine (DETA), or other polyamines. Exemplary examples include Quadrols, Tetrols, Pentrols available from BASF. Suitable alkanolamines include, without limitation, monoethanolamine (MEA), diethanolamine (DEA), reactions products of MEA and/or DEA with coconut oils and acids.

EXPERIMENTS OF THE DISCLOSURE Comparative Example 1

This example illustrates a control sand slurry including sand precoated with 0.5% v/w of an organo siloxane solution and slurried in the absence of an aldehyde enhancing proppant suspending agent.

The control slurry was composed of sand precoated with a 0.5% v/w of a blend of organo siloxane per weight of sand (KSS-8), 0.1% v/v anionic friction reducer KGFR-1 (brine based), and 48% w/v of 40:70 mesh sand in 200 mL of 100% produced Marcellus water as a control. The control slurry was sheared in a 1 liter blender jar @ 6500 RPM for 2 minutes. The control slurry showed less than 5% suspended sand as shown in FIG. 1 .

Example 1

This example illustrates a slurry including sand precoated with 0.5% v/w of an organo siloxane solution and slurried in the presence of 50 ppm of an aldehyde enhancing proppant suspending agent.

The slurry was composed of 0.1% v/v anionic friction reducer KGFR-1 (brine based), 50 ppm a glutaraldehyde enhancing suspending agent, and 48% w/v of 40:70 mesh sand precoated with 0.5% v/w of a blend of organo siloxane per weight of sand (KSS-8) in 200 mL of 100% produced Marcellus water. The slurry was sheared in a 1 liter blender jar @ 6500 RPM for 2 minutes. The slurry with the enhancing suspending agent showed greater than 50% suspended sand as shown in FIG. 2 .

Comparative Example 2

This example illustrates a control sand slurry including sand precoated with 1.0% v/w of an organo siloxane solution slurred in the absence of an aldehyde enhancing proppant suspending agent.

The control slurry was composed of 1.0% v/w of a blend of organo siloxane per weight of sand (KSS-8), 0.1% v/v anionic friction reducer KGFR-1 (brine based), and 48% w/v 40:70 mesh Sand in 200 mL in 100% produced Marcellus water. The control slurry was sheared in a 1 liter blender jar @ 6500 RPM for 2 minutes. The control slurry showed less than 5% suspended sand as shown in FIG. 3 .

Example 2

This example illustrates a sand slurry including sand precoated with 1.0% v/w of an organo siloxane solution slurried in the presence of 50 ppm of an aldehyde enhancing proppant suspending agent.

The slurry was composed of 0.1% v/v anionic friction reducer KGFR-1 (brine based), 50 ppm glutaraldehyde enhancing proppant suspending agent, and 48% w/v 40:70 mesh sand precoated with 1.0% v/w of a blend of organo siloxane per weight of sand (KSS-8) in 200 mL in 100% produced Marcellus water. The slurry was sheared in a 1 liter blender jar @ 6500 RPM for 2 minutes. The slurry with the enhancing proppant suspending agent showed greater than 85% suspended sand as shown in FIG. 4 .

Example 3

This example illustrates analysis of the produced Marcellus water.

TABLE I Water Analysis to Determine Dissolved Solids Anions mg/L meq/L Cations mg/L meq/L Chlorides 84854.10 2392.89 Sodium 28730.00 1249.76 Sulfate 0.00 0.00 Calcium 14630.00 731.50 Bicarbonates 24.40 0.40 Magnesium 1451.00 119.42 Carbonates 0.00 0.00 Barium 621.70 9.08 Hydroxide 0.00 0.00 Strontium 2125.00 48.50 Phosphate 0.00 0.00 Potassium 110.90 2.84 Silica 0.00 0.00 Iron 103.30 5.55 Chromium 0.00 0.00 pH 5.48 Manganese 0.00 0.00

TABLE II Water Analysis to Determine Hard Water Components CaSO₄ Concentration Scaling Index of CaCO₃* and Calculated Solubility** SI Concentration 0.000 meq/L 30° C. −1.4041 30° C. 16.245 meq/L 50° C. −0.9215 50° C. 15.949 meq/L 80° C. 0.0949 80° C. 15.729 meq/L *Scaling is probable if SI is greater than 0, Severity increasing with higher SI values **Scaling is probable if concentration is greater than calculated solubility

FIG. 5 shows that result of SI testing of CaCO₃ scale tendency at a temperature ranging from 0° C. to 80° C. The SI scale is measured scale tendency of a solution. Solution having an SI<0 means that scale formation is unlikely, while a solution having a SI>0 means that scale formation is indicated. FIG. 6 shows that the calculated CaSO₄ solubility as a function of temperature.

TABLE III Theoretical Values of Scale CaCO₃ mg/L CaSO₄ mg/L BaSO₄ mg/L 30° C. 0.0 30° C. 0.0 25° C. 0.0 40° C. 0.0 40° C. 0.0 50° C. 0.0 50° C. 0.0 50° C. 0.0 65° C. 0.0 60° C. 0.0 60° C. 0.0 80° C. 0.0 70° C. 0.0 70° C. 0.0 95° C. 0.0 80° C. 8.6 80° C. 0.0

The produced water had a specific gravity (SG) was 1.111 and have a boron content of 219.1 mg/L.

All references cited herein are incorporated by reference. Although the disclosure has been disclosed with reference to its preferred embodiments, from reading this description those of skill in the art may appreciate changes and modification that may be made which do not depart from the scope and spirit of the disclosure as described above and claimed hereafter. 

We claim:
 1. A method comprising: pumping or injecting, into a formation under fracturing conditions, a fracturing fluid comprising: an aqueous base fluid including at least 5,000 ppm total dissolved solids, a friction reducer, a high viscosity friction reducer, or mixtures thereof, an effective amount of an enhancing proppant suspending composition comprising: one or more aldehydes, one or more ketones, or mixtures or combinations thereof, one or more hydrophobic modified proppants, and no ammonium based quaternary salts, wherein the effective amount is between about 1 ppm and 1,000 ppm and is sufficient to suspend the one or more hydrophobic modified proppants in the fracturing fluid reducing proppant settling during the pumping or injecting step.
 2. The method of claim 1, wherein, in the pumping or injecting step: the one or more aldehydes comprising compounds of the formula: R—CHO R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms; the one or more ketones comprising compounds of the formula: R′—C(O)—R″ R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), and one or more of the carbon atoms may be replaced by oxygen atoms.
 3. The method of claim 2, wherein, in the pumping or injecting step: the aldehydes comprising formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, the ketones comprising acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof.
 4. The method of claim 1, wherein, in the pumping or injecting step: the aqueous base fluid comprising a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof.
 5. The method of claim 1, wherein, in the pumping or injecting stem: the fracturing fluid further comprising one or more viscosifying agents.
 6. The method of claim 5, wherein, in the pumping or injecting stem: the fracturing fluid further comprising: one or more crosslinking agents comprising borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and one or more crosslinking delay agents.
 7. The method of claim 1, wherein, in the pumping or injecting step: the one or more hydrophobic modified proppants comprising one or more hydrophobic resin-coated proppants.
 8. The method of claim 1, wherein, in the pumping or injecting step: the one or more hydrophobic modified proppants comprising one or more proppants coated with a coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.
 9. The method of claim 1, wherein, in the pumping or injecting step: the fracturing fluid further comprising: a hydrophobic coating composition comprising: an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures thereof, the hydrophobic coating composition coats one or more proppants in situ to form the one or more hydrophobic modified proppants.
 10. A method comprising: pumping or injecting, into a formation under fracturing conditions, a first fracturing fluid comprising: an aqueous base fluid including at least 5,000 ppm total dissolved solids, one or more friction reducers, and no proppant, and pumping or injecting, into the formation under fracturing conditions, a second fracturing fluid comprising: an aqueous base fluid including at least 5,000 ppm total dissolved solids, a friction reducer, a high viscosity friction reducer, or mixtures thereof, an effective amount of an enhancing proppant suspending composition comprising: one or more aldehydes, one or more ketones, or mixtures or combinations thereof, one or more hydrophobic modified proppants, and no ammonium based quaternary salts, and wherein the effective amount is between about 1 ppm and 1,000 ppm and is sufficient to suspend the one or more hydrophobic modified proppants in the fracturing fluid reducing proppant settling during the second pumping or injecting step.
 11. The method of claim 10, wherein, in the second or injecting pumping step: the one or more aldehydes comprising compounds of the formula: R—CHO R is a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ aldehydes), and one or more of the carbon atoms may be replaced by oxygen atoms, the one or more ketones comprising compounds of the formula: R′—C(O)—R″ R′ and R″ are independently a hydrocarbyl group having between 1 and about 40 carbon atoms (C₁-C₄₀ ketones), and one or more of the carbon atoms may be replaced by oxygen atoms.
 12. The method of claim 11, wherein, in the second pumping or injecting step: the aldehydes comprising formaldehydes, ethanal, propanals, butanals, pentanals, hexanals, heptanals, octanals, nonanals, decanals, undecanals, dodecanals, tridecanals, tetradecanals, pentadecanals, higher alkanals, substituted analogs thereof, and mixtures or combinations thereof, in the ketones comprising acetone, butanones, pentanones, pentanones, hexanones, heptanones, octanones, nonanones, decanones, undecanones, dodecanones, tridecanones, tetradecanones, pentadecanones, higher alkanones, substituted analogs thereof, and mixtures or combinations thereof.
 13. The method of claim 10, wherein, in the first and second pumping or injecting steps: the aqueous base fluids comprising a brackish water, a produced water, a flow back water, a reclaimed water, or mixtures and combinations thereof.
 14. The method of claim 10, wherein, in the first and second pumping or injecting steps: the first fracturing fluid further comprising one or more viscosifying agents, and/or the second fracturing fluid further comprising one or more viscosifying agents.
 15. The method of claim 14, wherein, in the first and second pumping or injecting steps: the first fracturing fluid further comprising: one or more crosslinking agents comprising borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and one or more crosslinking delay agents or a mixture of crosslinking delay agents, the second fracturing fluid further comprising: one or more crosslinking agents comprising borates, borates related crosslinkers, zirconates, zirconate derivatives, aluminates, aluminate derivatives, or mixtures thereof, and one or more crosslinking delay agents.
 16. The method of claim 10, wherein, in the second pumping or injecting step: the one or more hydrophobic proppants comprising one or more hydrophobic resin-coated proppants.
 17. The method of claim 10, wherein, in the second pumping or injecting step: the one or more hydrophobic modified proppants comprising one or more proppants coated with a coating composition comprising an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures and combinations thereof.
 18. The method of claim 10, wherein, in the second pumping or injecting step: the second fracturing fluid further comprising: a coating composition comprising: an organosilane, a fluoro-organosiloxane, a fluoro-organosilane, a siloxane, or mixtures thereof, the hydrophobic coating composition coats the one or more proppants in situ to form the one or more hydrophobic modified proppants.
 19. The method of claim 10, wherein, in the first pumping or injecting step: the first fracturing fluid further comprising one or more quaternary salts comprising compounds of the general formula: R¹R²R³ArN⁺X⁻ R′, R², and R³ are the same or different and are hydrogen atoms or substitutes selected from the group consisting of carbyl groups, hydrocarbyl groups, alkyl groups, aryl groups, alkaaryl groups, aralkyl groups, and mixtures thereof having between 1 and 40 carbon atoms, wherein one or more of the carbon atoms may be replace by an oxygen atom, Ar is an aryl group, alkaaryl groups, aralkyl groups, and mixtures thereof having between 5 and 40 carbon atoms, wherein one or more of the carbon atoms may be replaced with an oxygen atom, a nitrogen atom, a sulfur atoms, or mixtures thereof, and X⁻ is a counterion. 